Solutions of poly(ether ether ketone) in dichloroacetic acid have been shown to form monolithic, thermoreversible gels at temperatures ranging from 10 to 140 °C. A phase diagram was constructed over broad concentration and temperature ranges, and the phase boundary suggests an upper critical solution temperature (UCST) behavior. Furthermore, poly(ether ether ketone) (PEEK) gels were solvent-exchanged with water to form hydrogels and subsequently lyophilized to form PEEK aerogels. The PEEK aerogels of density 0.2 g/mL were found to be highly porous and composed of uniform 200 nm morphological features. The crystal structure of the PEEK hydrogels and aerogels was found to be identical to that of melt-crystallized PEEK. The mechanical properties of the PEEK aerogels (in compression) were found to be superior to conventional silicate aerogels of comparable density. This report is the first example of a monolithic, thermoreversible gel of PEEK and the first demonstration of PEEK hydrogels and aerogels.